CN103801188B - A kind of Wet Fgd By Limestone With Additives and preparation method thereof - Google Patents
A kind of Wet Fgd By Limestone With Additives and preparation method thereof Download PDFInfo
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- CN103801188B CN103801188B CN201410072548.7A CN201410072548A CN103801188B CN 103801188 B CN103801188 B CN 103801188B CN 201410072548 A CN201410072548 A CN 201410072548A CN 103801188 B CN103801188 B CN 103801188B
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Abstract
The invention discloses a kind of Wet Fgd By Limestone With Additives, comprise following raw material: adipic acid 60 ~ 70 parts, natrium citricum 5 ~ 10 parts, Sodium Benzoate 5 ~ 10 parts, lanthanum nitrate 2 ~ 3 parts, sodium acetate 5 ~ 10 parts, 5 ~ 10 parts, magnesia, 3 ~ 5 parts, magnesium sulfate; Raw material is added water respectively, heating water bath is to aqueous solution being obtained composite solution after each components dissolved; Be cooled to room temperature after composite solution heating water bath, utilize Vacuum Freezing & Drying Technology to obtain desulfurizing agent.Inventive desulfurization additive, without the need to changing existing coal burning flue gas desulphurization unit, to sulfur content 2000 ~ 14000mg/Nm
3coal combustion gas especially 4000 ~ 14000mg/Nm
3sulphur coal combustion gas there is remarkable desulfuration effect, improve the quality of limestone utilization, desulfuration efficiency and by-produced gypsum, have and prevent desulphurization system fouling effect significantly, reduce power consumption, strengthen coal adaptability advantage.
Description
Technical field
The present invention relates to a kind of wet desulfurizing process, be specifically related to a kind of Wet Fgd By Limestone With Additives and preparation method thereof, belong to chemical field.
Background technology
Wet Flue Gas Desulfurization Technology (being called for short FGD) is that current domestic application is the widest, desulfuration efficiency is the highest, runs the most stable sulfur removal technology, and byproduct can be recycled, and has good environmental benefit, accounts for more than 90% of the domestic desulfurizer built at present.But, the enforcement of desulfurization discharge standard new due to country and the strict demand for key area discharge, the design objective of existing equipment can not meet the requirement of existing discharge standard far away; Meanwhile, along with the prolongation of running time, the decline of equipment performance, inevitably there will be the phenomenon of desulfuration efficiency decline and desulfurizer fouling; In addition, for the consideration of business efficiency, use the situation of sulphur coal to increase gradually, a lot of existing wet desulphurization device cannot meet the environmental protection standard requirement of increasingly stringent.
Transformation beyond doubt a kind of means improving desulfuration efficiency are carried out to original desulfurizer, although this kind of means can improve the performance of device, but cost often reaches more than 50% of original device cost; Further, once combustion sulfur content of coal increases or environmental protection standard improves, also certainly will to transform device and cause and constantly increase cost.
Improving desulfuration efficiency by sulfur-removing additives is the means that present industrialization desulfuration field is mainly applied.At present, in existing sulfur-removing additives, desulfuration efficiency can be significantly improved; But, existing sulfur-removing additives only for sulfur content at 1000 – 3000 mg/Nm
3the coal-fired flue-gas of (CN 103055690A, CN103386248A, CN102419359) has significant desulfurized effect; But, in actual applications, because raw material ground sulfur content of coal is higher, or improve the reasons such as sulphur coal proportioning according to economic needs and to cause in coal-fired flue-gas sulfur content considerably beyond 3000mg/Nm
3, even can reach 10000 mg/Nm
3above, existing sulfur-removing additives can not meet the discharge standard of national new regulation, therefore, is badly in need of wanting a kind of sulfur-removing additives gone in the high Wet FGD of coal sulfur content.
Summary of the invention
Technical problem to be solved by this invention provides a kind of Wet Fgd By Limestone With Additives and preparation method thereof, without the need to making any change to existing coal burning flue gas desulphurization unit, is 2000 ~ 14000mg/Nm to sulfur content
3coal combustion gas especially 4000 ~ 14000mg/Nm
3sulphur coal combustion gas there is significant desulfurized effect; Improve the clearance of sulfur dioxide, improve the utilization rate of lime stone and the quality of by-produced gypsum, have simultaneously and prevent desulphurization system fouling effect significantly, there is the advantage reducing power consumption and strengthen coal adaptability.
Based on above-mentioned opinion, the present invention is achieved in that
A kind of Wet Fgd By Limestone With Additives, comprises the raw material of following weight: adipic acid 60 ~ 70 parts, natrium citricum 5 ~ 10 parts, Sodium Benzoate 5 ~ 10 parts, lanthanum nitrate 2 ~ 3 parts, sodium acetate 5 ~ 10 parts, 5 ~ 10 parts, magnesia, 3 ~ 5 parts, magnesium sulfate.
Further, described adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, sodium acetate, magnesia, magnesium sulfate are technical grade chemicals; Wherein, described magnesium sulfate is magnesium sulfate monohydrate, and described sodium acetate is anhydrous sodium acetate, and described adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, magnesia is not all containing the crystallization water.
Further, sulfur-removing additives of the present invention is applied to limestone wet-process coal burning flue gas desulphurization unit.
Further, the coal-fired flue-gas sulfur content of described limestone wet-process coal burning flue gas desulphurization unit is 2000 ~ 14000 mg/Nm
3.
Further, the coal-fired flue-gas sulfur content of described limestone wet-process coal burning flue gas desulphurization unit is 4000 ~ 14000 mg/Nm
3.
Further, the addition first of described sulfur-removing additives is 0.05 ~ 0.08% of lime stone slurry weight, and later every day supplements 8 ~ 13% of addition first and can ensure that sweetening process is carried out smoothly.
The present invention also provides a kind of method preparing above-mentioned sulfur-removing additives, comprise the following steps: accurately take adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, sodium acetate, magnesia, magnesium sulfate in proportion, to add water respectively and heating water bath is stirred to each components dissolved at 50 ~ 55 DEG C; By the aqueous solution of each component obtained composite solution together; Room temperature is cooled to after composite solution being placed in 70 ~ 75 DEG C of water-bath still agitating heating 1 ~ 2h, the quick freezing repository above-mentioned complex liquid being placed in-20 ~-40 DEG C cools the temperature to-30 ~-35 DEG C and maintains 1h in 4h, then the mixture after freezing is placed in the vacuum storehouse of vacuum at 25-50Pa, and in 30min, vacuum is adjusted to 30Pa, open heating system makes temperature rise to 0 ~ 5 DEG C in 2 ~ 3h, and maintains 2 ~ 5h at this temperature; Then in 0.5 ~ 1h, make temperature rise to 35 ~ 40 DEG C, and maintain 1 ~ 2h at this temperature, after closing vacuum system recovery normal pressure, obtain the sulfur-removing additives that water content is less than 0.1%.
Hinge structure of the present invention has following remarkable result:
(1) hexanedioic acid of the present invention, natrium citricum, Sodium Benzoate, sodium acetate etc. are containing hydrophilic functional groups and hydrophobic functional group, there is surface-active action, the sinking speed of particle in liquid matter surface tension, minimizing slurry viscosity, the dispersiveness increasing solid particle in slurries and solubility, reduction slurries can be reduced, thus improve spray atomizing quality, strengthening mass transfer promotes the absorption of the dissolving of lime stone and sulfur dioxide, decreases gas phase and liquid phase resistance, reaches the effect improving the clearance of sulfur dioxide and the utilization rate of lime stone;
(2) pH value of Organic weak acid or base mixture of the present invention to lime stone slurry has very strong cushioning effect, the acidity of slurries can be maintained for a long time at pH about 5.5, this acidity is the optimum acidity of desulphurization system, thus can provide the stability that whole system is run;
(3) absorption of natrium citricum of the present invention to sulfur dioxide has very strong facilitation; In addition, natrium citricum has good complexing to calcium ion, magnesium ion, can accelerate the growth of gypsum crystallization particle, thus prevents the fouling of wet desulfurization of flue gas by limestone-gypsum method apparatus system;
(4) magnesia of the present invention, except itself having the absorption of sulfur dioxide, can generate magnesium sulfate and continues contribution and increase sulfate ion, successful time higher to coal-fired sulfur content in the environment on absorption tower;
(5) lanthanum nitrate of the present invention is as catalytic oxidant, the calcium sulfite rapid oxidation generated can be become calcium sulfate, improve the utilization ratio of oxidation air in catalytic process; Meanwhile, the complex reaction of natrium citricum and magnesian conversion reaction are had to the catalytic action accelerating reaction process;
(6) Vacuum Freezing & Drying Technology is adopted in the preparation method of inventive desulfurization agent, material moisture under low temperature, low pressure directly distils, and substantially completely cut off air, therefore restrained effectively heat-sensitive substance and biological, chemical or physical change occur, physical arrangement and the molecule structure change of material are minimum, and performance is substantially unchanged; There is not Surface hardened layer problem in the material reducing water content, and its inner formation porous is spongy, thus has excellent rehydration; Use Vacuum Freezing & Drying Technology material handling, farthest can keep the property of medicine of medicine, improve raw material degree of mixing, reduce moisture.
Therefore, the present invention is under the prerequisite without the need to carrying out any change to existing apparatus, adopt interpolation Desulfurization synergist of the present invention can improve desulfuration efficiency significantly, reduce energy consumption to a certain extent, improve blending ratio, reduce equipment scaling, improve by-produced gypsum quality, strengthen coal adaptability, select for power plant provides a kind of new energy-saving and emission-reduction; Not only to sulfur content 2000 ~ 4000 mg/Nm
3coal-fired flue-gas successful, desulfuration efficiency can improve 5-10 percentage point; And be 4000 ~ 14000 mg/Nm for sulfur content
3high-sulfur coal-fired flue gas desulfurization effect especially remarkable, desulfuration efficiency is the highest can reach 99.5%.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with embodiment, technical scheme of the present invention is set forth in detail.But, persons of ordinary skill in the art may appreciate that in each embodiment of the present invention, proposing many ins and outs to make reader understand the application better.But, even without these ins and outs with based on the many variations of following embodiment and amendment, each claim of the application technical scheme required for protection also can be realized.
Embodiment 1:
The first embodiment relates to a kind of Wet Fgd By Limestone With Additives, for improve the higher desulfurizer of sulfur content desulfuration efficiency, prevent scaling, strengthen coal adaptability, reduce power consumption.
In the present embodiment, this sulfur-removing additives comprises the raw material of following weight: adipic acid 65 parts, natrium citricum 8 parts, Sodium Benzoate 7 parts, lanthanum nitrate 3 parts, sodium acetate 7 parts, 8 parts, magnesia, 4 parts, magnesium sulfate.Wherein adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, sodium acetate, magnesia, magnesium sulfate are technical grade chemicals; Magnesium sulfate is magnesium sulfate monohydrate, and sodium acetate is anhydrous sodium acetate, and adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, magnesia is not all containing the crystallization water.
In the absorption tower slurries of desulfurizer, add the sulfur-removing additives of present embodiment specifically, when adding first, control additive concentration controls concentration in slurries is 0.05 ~ 0.08% of lime stone slurry weight, is generally added by absorption tower drain.Concrete concentration controls to regulate according to coal property, desulfurizer liquid-gas ratio etc., supplements 8 ~ 13% of addition first afterwards every day, making up smoke evaporative, produce gypsum, additive that discharge of wastewater causes runs off.
Example illustrates:
(1) in the practical application of certain power plant's 300,000 kilowatts of unit, former desulfurizer design entry sulfur dioxide in flue gas content is up to 2500mg/Nm
3, it is 90% that two slush pumps can maintain desulfuration efficiency, outlet sulfur dioxide concentration 250 mg/Nm
3lower than the former regulated discharge standard (400mg/Nm of country
3); And use desulfurizing agent of the present invention, first interpolation 1 ton, after this supplement 80-130kg every day, desulfuration efficiency can reach more than 96%, outlet sulfur dioxide concentration 100mg/Nm
3lower than the up-to-date regulated discharge standard (200mg/Nm of country
3).
Table 1: use inventive desulfurization agent on the impact of coal-fired flue gas desulfurization efficiency
As shown in Table 1, use inventive desulfurization agent, desulfuration efficiency can reach more than 96%, and desulfuration efficiency improves 6 percentage points, meets the emission compliance that country is new.
(2) certain power plant former design desulphurization system sulfur dioxide entrance concentration 2500mg/Nm
3, desulfuration efficiency 92%.Meet national emission request.In certain period, because coal-fired cost rises, adopt sulphur coal, sulfur dioxide in flue gas content reaches 4200-4500mg/Nm
3, desulfurization degree is only 80%, superstate regulation far away; Use sulfur-removing additives of the present invention, first interpolation 1.5 tons, after this supplement 120-150kg every day, desulfuration efficiency is as shown in table 2:
Table 2: use inventive desulfurization agent on the impact of coal-fired flue gas desulfurization efficiency
As shown in Table 2, use inventive desulfurization agent, desulfuration efficiency can reach 99%, and desulfuration efficiency improves 19 percentage points, has both adapted to Coal rank, also meets national emission compliance simultaneously.
(3) in the 600000 kilowatts of unit practical applications of certain factory, former desulfurizer design entry flue gas content is 4000 mg/Nm
3, but need three slush pumps to run could to maintain desulfuration efficiency be 96% qualified discharge simultaneously; Use sulfur-removing additives of the present invention, first interpolation 2.5 tons, after this supplement 200-250kg every day, desulfuration efficiency is as shown in table 3:
Table 3: use inventive desulfurization agent on the impact of coal-fired flue gas desulfurization efficiency
As shown in Table 3, use desulfurizing agent of the present invention, desulfuration efficiency brings up to 99.5%; Now, use two slush pumps also can exceed former design standard, desulfuration efficiency reaches 98%; Outlet sulfur dioxide concentration 80 mg/Nm
3lower than the up-to-date regulated discharge standard (200mg/Nm of country
3), also meet the green needs produced; Accomplishing the dual-purpose standby of equipment, not only saved station service, and substantially increase equipment security of operation level, also having laid the foundation for meeting strict emission standards more simultaneously.
(4) in the application of power plant of high pollution control area 600,000 kilowatts of units, former desulfurizer design sulfureous in flue gas content is 10000 mg/Nm
3, the while of four slush pumps, operational efficiency is 95%, but outlet sulfur dioxide concentration 500 mg/Nm
3higher than country former permission regulated discharge standard (400mg/Nm
3); Use this additive, first interpolation 2.4 tons, after this supplement 200-300kg every day, desulfuration efficiency is as shown in table 4:
Table 4: use inventive desulfurization agent on the impact of coal-fired flue gas desulfurization efficiency
As shown in Table 4, use desulfurizing agent of the present invention, desulfuration efficiency is up to 99.5%, and in the case, close a slush pump, desulfuration efficiency still brings up to 99.0%, and exit concentration is lower than 100 mg/Nm
3meet national up-to-date regulated discharge standard (200mg/Nm
3).
(5) in the application of another certain power plant's 600,000 kilowatts of units of sulphur coal area, former desulfurizer design sulfureous in flue gas content is 11000 mg/Nm
3, four slush pumps run desulfuration efficiency 96% simultaneously; But because ageing equipment and other reasons cause desulfuration efficiency to be down to 92%, have to use instead mix burn low-sulfur coal make sulfureous in flue gas content lower than 6000 mg/Nm
3ability is qualified discharge reluctantly, and cost significantly improves.Use this additive, first interpolation 2.5 tons, after this supplement 200-300kg every day, desulfuration efficiency is as shown in table 5:
Table 5: use inventive desulfurization agent on the impact of coal-fired flue gas desulfurization efficiency
As shown in Table 5, for the flue gas of ultra-high-sulfur(UHS) content, after using desulfurizing agent of the present invention, original device desulfuration efficiency can reach 98.6%, even if when stopping using a slush pump, desulfuration efficiency also reaches 97%, even if use sulphur coal (sulfureous in flue gas content 15000 mg/Nm
3) outlet drain sulfur dioxide concentration is 450mg/Nm
3below, not only meet New emission standard, meanwhile, only stop mixing burning fat coal one, annual saving reaches more than 6,000 ten thousand yuan.
Various situation illustrates above, after use sulfur-removing additives of the present invention, and a slush pump of stopping using, absorption tower pressure drop reduces about 20%, reduces station service 7-10%, achieves and do not increase the effect that operating cost but reaches energy-saving and emission-reduction; In addition, in actual applications, owing to can suitably improve electric sulfur content of coal, more use colms, improve the flexibility that power plant purchases coal, greatly reduce operating cost.
Embodiment 2:
The second embodiment of the present invention relates to a kind of preparation method of Wet Fgd By Limestone With Additives, and concrete steps are as follows:
Accurately take the following raw material of following weight portion: adipic acid 60 ~ 70 parts, natrium citricum 5 ~ 10 parts, Sodium Benzoate 5 ~ 10 parts, lanthanum nitrate 2 ~ 3 parts, sodium acetate 5 ~ 10 parts, 5 ~ 10 parts, magnesia, 3 ~ 5 parts, magnesium sulfate; Wherein adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, sodium acetate, magnesia, magnesium sulfate are technical grade chemicals, magnesium sulfate is magnesium sulfate monohydrate, sodium acetate is anhydrous sodium acetate, and adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, magnesia is not all containing the crystallization water; Each raw material number adjusts according to coal-fired flue-gas amount.
Above-mentioned raw materials to be added water respectively and heating water bath is stirred to each components dissolved at 50 ~ 55 DEG C; By the aqueous solution of each component obtained composite solution together; Room temperature is cooled to after composite solution being placed in 70 ~ 75 DEG C of water-bath still agitating heating 1 ~ 2h, the quick freezing repository above-mentioned complex liquid being placed in-20 ~-40 DEG C cools the temperature to-30 ~-35 DEG C and maintains 1h in 4h, then the mixture after freezing is placed in the vacuum storehouse of vacuum at 25-50Pa, and in 30min, vacuum is adjusted to 30Pa, open heating system makes temperature rise to 0 ~ 5 DEG C in 2 ~ 3h, and maintains 2 ~ 5h at this temperature; Then in 0.5 ~ 1h, make temperature rise to 35 ~ 40 DEG C, and maintain 1 ~ 2h at this temperature, after closing vacuum system recovery normal pressure, obtain the sulfur-removing additives that water content is less than 0.1%.
The step of various method divides above, just in order to be described clearly, can merge into a step or splitting some step, being decomposed into multiple step, when realizing as long as comprise identical logical relation, all in the protection domain of this patent; To adding inessential amendment in algorithm or in flow process or introducing inessential design, but the core design not changing its algorithm and flow process is all in the protection domain of patent.
Be not difficult to find, present embodiment is the corresponding embodiment of the method for the first embodiment, and present embodiment can be worked in coordination with the first embodiment and be implemented.The relevant technical details mentioned in first embodiment is still effective in the present embodiment, in order to reduce repetition, repeats no more here.Correspondingly, the relevant technical details mentioned in present embodiment also can be applicable in the first embodiment.
Persons of ordinary skill in the art may appreciate that the respective embodiments described above realize specific embodiments of the invention, and in actual applications, various change can be done to it in the form and details, and without departing from the spirit and scope of the present invention.
Claims (6)
1. a Wet Fgd By Limestone With Additives, it is characterized in that, comprise the raw material of following weight portion: adipic acid 60 ~ 70 parts, natrium citricum 5 ~ 10 parts, Sodium Benzoate 5 ~ 10 parts, lanthanum nitrate 2 ~ 3 parts, sodium acetate 5 ~ 10 parts, 5 ~ 10 parts, magnesia, 3 ~ 5 parts, magnesium sulfate; The preparation method of described Wet Fgd By Limestone With Additives, adopt Vacuum Freezing & Drying Technology, comprise the steps: accurately to take adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, sodium acetate, magnesia, magnesium sulfate in proportion, to add water respectively and heating water bath is stirred to each components dissolved at 50 ~ 55 DEG C; By the aqueous solution of each component obtained composite solution together; Room temperature is cooled to after composite solution being placed in 70 ~ 75 DEG C of water-bath still agitating heating 1 ~ 2h, the quick freezing repository above-mentioned complex liquid being placed in-20 ~-40 DEG C cools the temperature to-30 ~-35 DEG C and maintains 1h in 4h, then the mixture after freezing is placed in the vacuum storehouse of vacuum at 25-50Pa, and in 30min, vacuum is adjusted to 30Pa, open heating system makes temperature rise to 0 ~ 5 DEG C in 2 ~ 3h, and maintains 2 ~ 5h at this temperature; Then in 0.5 ~ 1h, make temperature rise to 35 ~ 40 DEG C, and maintain 1 ~ 2h at this temperature, after closing vacuum system recovery normal pressure, obtain the sulfur-removing additives that water content is less than 0.1%.
2. Wet Fgd By Limestone With Additives according to claim 1, is characterized in that, described adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, sodium acetate, magnesia, magnesium sulfate are technical grade chemicals; Wherein, described magnesium sulfate is magnesium sulfate monohydrate, and described sodium acetate is anhydrous sodium acetate, and described adipic acid, natrium citricum, Sodium Benzoate, lanthanum nitrate, magnesia is not all containing the crystallization water.
3. Wet Fgd By Limestone With Additives according to claim 1, is characterized in that, described sulfur-removing additives is applied to limestone wet-process coal burning flue gas desulphurization unit.
4. Wet Fgd By Limestone With Additives according to claim 3, is characterized in that, the coal-fired flue-gas sulfur content of described limestone wet-process coal burning flue gas desulphurization unit is 2000 ~ 14000 mg/Nm
3.
5. Wet Fgd By Limestone With Additives according to claim 4, is characterized in that, the coal-fired flue-gas sulfur content of described limestone wet-process coal burning flue gas desulphurization unit is 4000 ~ 14000 mg/Nm
3.
6. Wet Fgd By Limestone With Additives according to claim 3, is characterized in that, the addition first of described sulfur-removing additives is 0.05 ~ 0.08% of lime stone slurry weight, and the 8-13% that later every day supplements addition first completes to desulfurization.
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| CN104645816A (en) * | 2015-01-28 | 2015-05-27 | 上海水平衡环境科技发展有限公司 | Wet desulphurization synergist |
| CN107648998A (en) * | 2017-11-13 | 2018-02-02 | 盐城工学院 | A kind of oxidized form compound additive for Wet Fgd By Limestone and preparation method thereof |
| CN107824039A (en) * | 2017-12-04 | 2018-03-23 | 中晶环境科技股份有限公司 | Composite oxidant and the method for dry desulfurization denitration |
| CN113814002B (en) * | 2020-06-18 | 2024-04-26 | 中国石油化工股份有限公司 | Coal-fired catalyst and preparation method and application thereof |
| CN112915747B (en) * | 2021-02-02 | 2023-04-18 | 华能山东能源工程有限公司 | Limestone-gypsum wet flue gas desulfurization composite additive and preparation method and application thereof |
| CN116808814A (en) * | 2023-06-13 | 2023-09-29 | 北京联发迈通科技有限公司 | Efficient composite desulfurization synergist and preparation process thereof |
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| CN103157370B (en) * | 2013-03-11 | 2015-01-21 | 上海申欣环保实业有限公司 | Desulfuration additive and manufacturing method thereof |
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